羰基化合物直接还原胺化合成伯胺催化剂研究进展

胺类化合物是一类重要的化工原料和中间体，在农药、医药、染料、高分子聚合物等领域有着广泛的应用。通过羰基化合物（醛或酮类）的还原胺化来制备胺类化合物是当前的研究热点。研究表明，贵金属基和非贵金属基的多相和均相催化剂均能够高效催化醛或酮类的还原胺化反应。本文对近年来羰基化合物直接还原胺化（或一锅法）合成伯胺的研究现状进行了综述，包括还原胺化反应、催化剂、反应条件、底物适用范围和催化作用机制等，其中重点阐述了直接还原胺化催化剂的研究进展。文章指出：通常多相催化剂具有活性高以及可重复使用等优点，而均相催化剂的优势在于催化效率高，伯胺选择性高；另一方面，以Pd、Rh、Ru等为代表的贵金属催化剂催化性能优异，但价格昂贵，因此可采用Co、Ni等性能同样优异但价格相对低廉的非贵金属催化剂以降低成本。文中提出，催化效率高、反应条件温和、普适性高的羰基化合物还原胺化催化剂应成为未来重点研究方向。     

脂肪伯胺在多行业中的应用简介

介绍了脂肪伯胺类产品在国内生产发展和现状、伯胺产品性能,以及在主要应用领域的应用及方法,为各领域用户提供应用上的指导。     

Leuckart还原胺化法的应用进展

叙述了由醛、酮与氨、伯胺或仲胺以及甲酸或甲酸铵或甲酰胺等作为还原剂经还原胺化制备伯胺、仲胺和叔胺的Leuckart反应的应用进展,总结了催化剂、溶剂等反应条件的影响.指出应加强对催化Leuckart反应及非经典Leuckart反应条件如离子液体中的还原胺化研究,从而使该反应的条件更温和,产物收率更高,适用的化合物范围更广.     

还原法制备芳香胺的研究进展

介绍了芳硝基化合物还原制备芳香胺的主要方法以及各还原方法在芳硝基化合物还原中的应用。芳硝基化合物还原制备芳香胺的方法主要有催化加氢法、金属还原法、水合肼还原法、硫化碱还原法、电化学还原法、催化氢转移法、光催化还原法、葡萄糖还原法、酶催化还原法等。其中光催化还原法和还原酶还原法反应条件温和、符合有机化合物转化过程中所追求的环保"良性"与"绿色"的目标,具有很高的研究应用价值。     

还原法制备芳香胺的研究进展

介绍了芳硝基化合物还原制备芳香胺的主要方法以及各还原方法在芳硝基化合物还原中的应用。芳硝基化合物还原制备芳香胺的方法主要有催化加氢法、金属还原法、水合肼还原法、硫化碱还原法、电化学还原法、催化氢转移法、光催化还原法、葡萄糖还原法、酶催化还原法等。其中光催化还原法和还原酶还原法反应条件温和、符合有机化合物转化过程中所追求的环保"良性"与"绿色"的目标,具有很高的研究应用价值。     

N，N′-二烷基聚醚胺用作封端异氰酸酯固化剂

1 前言 聚环氧烷多胺广泛应用于环氧固化剂、聚氨酯、聚脲及其他工业领域。这种胺类化合物通过相应的聚醚多元醇在氢气、氨和相应的催化剂(如Ni/Cu/Cr催化剂)的存在下还原胺化进行商业生产。这种聚醚胺通常含有一个柔软的相对分子质量为148～6000的聚醚骨架,如聚环氧乙烷二胺、     

水合肼法还原芳香硝基化合物制备芳胺的技术进展

综述了水合肼法还原芳香硝基化合物制备芳胺及其衍生物的近况,讨论了影响还原反应的主要因素和工艺条件,并展望了水合肼法制备芳胺工艺的应用前景和发展方向。     

俄罗斯脂肪胺生产及欧洲织物柔软剂应用进展

综述了俄罗斯脂肪胺生产技术,醛还原烷基化制伯胺,伯胺甲醛甲基化制叔胺及伯胺乙氧基化季铵化制乙氧基季铵盐。欧洲生产的乙氧基化季铵盐,咪唑啉阳离子ＳＡＡ及其在织物柔软剂上的应用进展,对国内叔胺生产工艺路线的选择和织物柔软剂开发品种提出了可行性建议。     

磺基甜菜碱的合成研究进展

磺基甜菜碱具有性能温和、界面活性高、抗二价阳离子能力强等优点,被广泛应用于洗涤剂、化妆品、石油开采等领域。本文介绍了以胺为原料,经叔胺化-季铵化两步法合成磺基甜菜碱的合成工艺进展,重点阐述了制备叔胺中间体的4种方法,即卤化胺化法、醇一步催化胺化法、甲醛加氢法和羰基还原胺化法。从原料性能、收率、环保性、可操作性等方面进行了分析比较,讨论了各方法存在的问题及工业化的可行性。此外,对叔胺中间体的季铵化过程中所用试剂3-氯-2-羟基丙磺酸钠和磺酸内酯进行了比较,最后指出羰基还原胺化法是实现绿色工业化生产应该努力的方向,而3-氯-2-羟基丙磺酸钠是一种经济、绿色、环保的季铵化试剂。     

非均相金属催化剂催化醇类还原胺化合成伯胺的研究进展

综述了近年来非均相金属催化剂在醇与NH_3还原胺化制备伯胺体系中的应用研究,重点阐述了醇胺化(包括缩合胺化和还原胺化)的反应机理,以及还原胺化制备伯胺所需催化体系的研究进展。醇的脱氢步骤是醇与氨还原胺化制备伯胺反应中的速率控制步骤,不同金属组分由于对NH_3与有机胺的吸附能不同而导致脱氢活性不同。在醇还原胺化制备伯胺的体系中,开发适用于无氢气条件下氢转移胺化的非均相催化剂、选择合适的载体、开发生物质醇合成伯胺的催化技术具有广阔的前景。     

高级脂肪胺及其衍生物的应用前景

简要介绍高级脂肪胺的种类、合成路线及性能。重点综述了高级脂肪伯胺和叔胺的应用,主要是在制备阳离子表面活性剂、非离子表面活性剂和两性表面活性剂等方面的应用;同时概述了仲胺、二胺、多胺及其衍生物的应用。最后对高级脂肪胺及其衍生物的发展提出了几点建议。     

脂肪胺生产和应用的一些新进展

本文介绍最近三年来脂肪胺生产和应用的某些进展。主要包括：用作洗涤剂活性物的新型非离子物－脂肪胺聚氧乙烯醚的应用研究以及脂肪醇一步法制长链叔胺新型催化剂的研究和应用。文中还简单介绍了脂肪胺工业应用的途径。     

醇法叔胺生产工艺质量控制

结合醇一步法叔胺生产实际情况,介绍了生产过程工艺及其对质量的影响因素,品质优越的叔胺生产是以高性能胺化催化剂及有效的工艺控制为保障条件。通过不同品种催化剂、工艺条件(温度、氢气分压等)对胺化反应进程的质量控制进行了讨论,认为胺化反应最终产物粗叔胺中伯/仲胺及残余醇的含量是影响成品质量的关键因素。     

单,双和三长链烷基叔胺及其季铵盐制备技术新进展

综述了单、双和三长链烷基叔胺及季铵盐的合成技术新进展。从传统的脂肪酸法，脂肪醇经氯代烷胺化法以及近年来国内外开发的新路线。重点介绍了脂肪醇常压一步法制叔胺的新方法，也涉及到脂肪肪酸甲酯、醇醚与原料催化胺化制叔胺的最新进展和各种路线的比较。     

脂肪叔胺制备技术进展

主要从3方面综述了脂肪叔胺制备技术的研发进展。介绍了脂肪叔胺的市场情况及主要用途,其主要作为制备阳离子表面活性剂和两性离子表面活性剂的重要中间体,这2类表面活性剂的主要品种可作为消毒杀菌剂、缓蚀剂、抗静电剂、织物整理剂以及个人护理用品中的活性成分等;重点阐述了脂肪叔胺的制备工艺过程,此工艺的技术关键是催化剂的制备,包括催化剂组分的筛选及其制备过程,目前主要采用的是多元金属复合催化剂,多以Cu与其他金属元素复合;简要回顾了脂肪醇催化胺化技术的发展概况,并对脂肪叔胺制备技术的进一步发展提出了建议。     

The Evolution of an Amine Dehydrogenase Biocatalyst for the Asymmetric Production of Chiral Amines

The reductive amination of ketones to produce chiral amines is an important transformation in the production of pharmaceutical intermediates. Therefore, industrially applicable enzymatic methods that enable the selective synthesis of chiral amines could be very useful. Using a phenylalanine dehydrogenase scaffold devoid of amine dehydrogenase activity, a robust amine dehydrogenase has been evolved with a single two‐site library allowing for the direct production of (R)‐1‐(4‐fluorophenyl)‐propyl‐2‐amine from para‐fluorophenylacetone with a k_cat value of 6.85 s⁻¹ and a K_M value of 7.75 mM for the ketone substrate. This is the first example of a highly active amine dehydrogenase capable of accepting aliphatic and benzylic ketone substrates. The stereoselectivity of the evolved amine dehydrogenase was very high (>99.8% ee) showing that high selectivity of the wild‐type phenylalanine dehydrogenase was conserved in the evolution process. When paired with glucose/glucose dehydrogenase, NADH cofactor can be effficiently regenerated and the reaction driven to over 93% conversion. The broad specificity, high selectivity, and near complete conversion render this amine dehydrogenase an attractive target for further evolution toward pharmaceutical compounds and subsequent application.     

脂肪醇催化胺化制叔胺工艺技术现状及前景

脂肪醇催化胺化制叔胺的工艺是目前生产脂肪叔胺的主要方法,和传统的酸法工艺相比具有明显的优势。该工艺的技术关键为胺化催化剂及工艺放大。催化剂的开发水平已经能够满足工业化生产的要求,但基础理论研究不够广泛的深入。要想进一步提高催化剂的水平。要从基础理论入手。工程放大主要是解决气、液、固三相之间的传质问题,可以通过反应器形式的改进来实现,如采用环路反应器及固定床反应器等。要从根本上解决国内目前叔胺生产厂家多但规模小的问题,需要在工程化问题上有所突破。     

Selective Hydrogenation of Fatty Nitriles to Primary Fatty Amines: Catalyst Evaluation and Optimization Starting from Octanenitrile

In this contribution, an evaluation of the potential of various homogeneous and heterogeneous catalysts for a selective hydrogenation of fatty nitriles toward primary amines is reported exemplified for the conversion of octanenitrile into octane‐1‐amine as a model reaction. When using heterogeneous catalysts such as the ruthenium catalyst Ru/C, the palladium catalyst Pd/C, and the platinum catalyst Pt/Al₂O₃, low selectivities in the hydrogenation are observed, thus leading to a large portion of secondary and tertiary amine side‐products. For example, when using Ru/C as a heterogeneous catalyst, high conversions of up to 99% are obtained but the selectivity remains low with a percentage of the primary amine being at 60% at the highest. The study further reveals a high potential of homogeneous ruthenium and manganese catalysts. When also taking into account economical considerations with respect to the metal price, in particular, manganese catalysts turn out to be attractive for the desired transformation and their application in the model reaction leads to the desired primary amine product with excellent conversion, selectivity, and high yield. Practical Applications: This work describes an optimized hydrogenation process for transforming fatty nitriles to their corresponding primary amines. In general, fatty amines belong to the most applied fatty acid‐derived compounds in the chemical industry with an annual product volume exceeding 800 000 tons per year in 2011 and are widely required in the chemical industry since such compounds are either directly used in home products such as fabric softeners, dishwashing liquids, car wash detergents, or carpet cleaners or in a broad range of industrial products, for example, lubricating additives, flotation agents, dispersants, emulsifiers, corrosion inhibitors, fungicides, and bactericides, showing additional major applications, e.g., in the detergents industry. Among them primary amines play an important industrial role. However, a major concern of current processes is the lack of selectivity and the formation of secondary and tertiary amines as side‐products. By modifying a recently developed catalytic system based on manganese as economically attractive and environmentally benign metal component an efficient and selective access to fatty amines when starting from the corresponding nitriles is achieved. For example, hydrogenation of octanenitrile leads to a synthesis of octane‐1‐amine with >99% conversion and excellent selectivity with formation of secondary and tertiary amine side‐products being suppressed to an amount of <1%.     

Biotransamination of Furan-Based Aldehydes with Isopropylamine: Enzyme Screening and pH Influence

Furan-based amines are highly valuable compounds which can be directly obtained via reductive amination from easily accessible furfural, 5-(hydroxymethyl)furfural (HMF) and 2,5-diformylfuran (DFF). Herein the biocatalytic amination of these carbonyl derivatives is disclosed using amine transaminases (ATAs) and isopropylamine (IPA) as amine donors. Among the different biocatalysts tested, the ones from Chromobacterium violaceum (Cv-TA), Arthrobacter citreus (ArS-TA), and variants from Arthrobacter sp. (ArRmut11-TA) and Vibrio fluvialis (Vf-mut-TA), afforded high levels of product formation (>80 %) at 100–200 mM aldehyde concentration. The transformations were studied in terms of enzyme and IPA loading. The pH influence was found as a key factor and attributed to the imine/aldehyde equilibrium that can arise from the high reactivity of the carbonyl substrates with a nucleophilic amine such as IPA.